EP0439040A1 - One-part primerless adhesive - Google Patents
One-part primerless adhesive Download PDFInfo
- Publication number
- EP0439040A1 EP0439040A1 EP91100367A EP91100367A EP0439040A1 EP 0439040 A1 EP0439040 A1 EP 0439040A1 EP 91100367 A EP91100367 A EP 91100367A EP 91100367 A EP91100367 A EP 91100367A EP 0439040 A1 EP0439040 A1 EP 0439040A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- adhesive
- ethylenically unsaturated
- acid
- component
- unsaturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 62
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 62
- 239000002253 acid Substances 0.000 claims abstract description 44
- 150000003673 urethanes Chemical class 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 11
- 239000004825 One-part adhesive Substances 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims description 19
- 239000004014 plasticizer Substances 0.000 claims description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims description 11
- 239000000454 talc Substances 0.000 claims description 11
- 229910052623 talc Inorganic materials 0.000 claims description 11
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 9
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 7
- 150000003254 radicals Chemical class 0.000 claims description 7
- 238000012644 addition polymerization Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 229910021485 fumed silica Inorganic materials 0.000 claims description 5
- OGBWMWKMTUSNKE-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C OGBWMWKMTUSNKE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003677 Sheet moulding compound Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- -1 alicyclic isocyanates Chemical class 0.000 description 23
- 239000012948 isocyanate Substances 0.000 description 23
- 239000005056 polyisocyanate Substances 0.000 description 21
- 229920001228 polyisocyanate Polymers 0.000 description 21
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 20
- 150000002513 isocyanates Chemical class 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 150000003077 polyols Chemical class 0.000 description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- 229920005862 polyol Polymers 0.000 description 10
- YKLUMGLEFOKZBY-UHFFFAOYSA-J tricarbamoyloxystannyl carbamate Chemical compound C(N)(=O)[O-].[Sn+4].C(N)(=O)[O-].C(N)(=O)[O-].C(N)(=O)[O-] YKLUMGLEFOKZBY-UHFFFAOYSA-J 0.000 description 10
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 description 4
- GTZCVFVGUGFEME-HNQUOIGGSA-N cis-Aconitic acid Natural products OC(=O)C\C(C(O)=O)=C/C(O)=O GTZCVFVGUGFEME-HNQUOIGGSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 2
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- JOOBVYPKYAURGD-UHFFFAOYSA-N 2-hydroxyethyl 2-methylidenepentanoate Chemical compound CCCC(=C)C(=O)OCCO JOOBVYPKYAURGD-UHFFFAOYSA-N 0.000 description 2
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 description 2
- GQTFHSAAODFMHB-UHFFFAOYSA-N 2-prop-2-enoyloxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOC(=O)C=C GQTFHSAAODFMHB-UHFFFAOYSA-N 0.000 description 2
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 2
- CIIWMXSMCCRQEQ-UHFFFAOYSA-N 3-phosphonooxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOP(O)(O)=O CIIWMXSMCCRQEQ-UHFFFAOYSA-N 0.000 description 2
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 235000017858 Laurus nobilis Nutrition 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 2
- 244000125380 Terminalia tomentosa Species 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 1
- OLQFXOWPTQTLDP-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCO OLQFXOWPTQTLDP-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical class OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 241000276498 Pollachius virens Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- KIBKSNLNGHPFTB-UHFFFAOYSA-L [acetyloxy(diethyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CC[Sn+2]CC KIBKSNLNGHPFTB-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- LYYNQLKRDKNQMN-UHFFFAOYSA-L [dodecanoyloxy(dimethyl)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](C)(C)OC(=O)CCCCCCCCCCC LYYNQLKRDKNQMN-UHFFFAOYSA-L 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- HRFMZHBXTDWTJD-UHFFFAOYSA-N dihexyltin Chemical compound CCCCCC[Sn]CCCCCC HRFMZHBXTDWTJD-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/06—Unsaturated polyesters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
- Y10T428/31601—Quartz or glass
Definitions
- This invention relates to structural acrylic urethane adhesives. Such adhesives are useful for bonding materials together in the assembly of automobiles. More specifically, this invention relates to an adhesive suitable for bonding fiberglass-reinforced polyester substrates.
- Transparent adhesives for glass which comprise urethane acrylates in acylic acid diluents, and which are suitable for the production of clear glass laminates are known and are described, for example, in U.S. Patent 4,717,739.
- such adhesives are not well suited for bonding fiberglass-reinforced polyester substrates, such as are useful, for example, in the manufacture of vehicles, particularly automobiles.
- SMC sheet molding compound
- this invention is a one-part adhesive which comprises a mixture of:
- this invention is a one-part adhesive which comprises a mixture of:
- this invention is a composite comprising a fiberglass-reinforced polyester substrate bonded to a second substrate, by means of a cured layer of a one-part adhesive between said substrates comprising a mixture of
- the adhesives of the invention, and the adhesive used in the composite of the invention are one-part adhesives which advantageously has high strength characteristics when used to bond fiberglass-reinforced polyester substrates without the use of a primer.
- the cured adhesives of this invention have a wide-ranging glass transition temperature which make them suitable for high and low temperature applications.
- the adhesives of the invention are thixotropic, heat-curable mixtures which, when cured, are graft copolymers of a urethane and vinyl polymers, wherein the vinyl portion contains pendant acid groups.
- the copolymer is prepared by copolymerizing an ethylenically unsaturated urethane polymer with an ethylenically unsaturated acid, acid salt, or anhydride.
- the mixture is preferably prepared with inhibitors which prevent the mixture from copolymerizing before application.
- the polymerizable ethylenically unsaturated urethane polymer component (hereafter "unsaturated urethane”) of the adhesive is a urethane polymer which has at least one unsaturation site which will copolymerize with the unsaturated acid, acid salt, or anhydride component.
- the unsaturated urethane preferably has a molecular weight of at least 1,000, more preferably at least 2,000, and most preferably at least 4,000; and is preferably no greater than 35,000, more preferably no greater than 15,000, and most preferably no greater than 10,000.
- the unsaturated urethane may be prepared by a variety of methods.
- this component may be prepared by contacting a polyisocyanate with an unsaturated hydroxy-functional reactant, optionally in the presence of additional active hydrogen-containing compounds and/or additional polyisocyanates.
- this component may also be prepared by contacting an unsaturated isocyanate with a hydroxy-functional reactant, optionally in the presence of additional active hydrogen-containing compounds and/or additional polyisocyanates.
- Isocyanates which are suitable for use in the preparation of the unsaturated urethane component include aromatic, aliphatic, cycloaliphatic, araliphatic, and heterocyclic polyisocyanates, and mixtures thereof, with alicyclic isocyanates as the most preferred for their stability in light.
- the isocyanate has a functionality of 2 to 4 isocyanate groups per molecule, more preferably of 2 to 3 isocyanate groups per molecule, and most preferably 2 isocyanate groups per molecule. Higher functionalities may also be used, but may cause excessive cross-linking, and result in an adhesive which is too viscous to handle and apply easily, and can cause the cured adhesive to be too brittle.
- isocyanates include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-and 1,4-diisocyanate and mixtures of these isomers; 1-isocyanato-3,3,5-trimethyl-5-isocyanato methyl cyclohexane (see e.g., German Auslegeschrift No.
- Patent 3,492,330 polyisocyanates containing allophanate groups of the type described, for example, in British Patent 994,890, in Belgian Patent 761,626 and in published Dutch Patent Application No. 7,102,524, polyisocyanates containing isocyanurate groups of the type described in German Patents 1,022,789; 1,222,067 and 1,027,394 and in German Offenlegungsschrift 1,929,034 and 2,004,048, polyisocyanates containing urethane groups of the type described, for example, in Belgian Patent 752,261 or in U.S.
- Patent 3,394,164 polyisocyanates containing acrylated urea groups as described in German Patent 1,230,778, polyisocyanates containing biuret groups of the type described, for example, in German Patent 1,101,392, in British Patent 889,050 and in French Patent 7,017,514, polyisocyanates obtained by telomerization reactions of the type described, for example, in Belgian Patent 723,640, polyisocyanates containing ester groups of the type described, for example, in British Patents 965,474 and 1,072,956, in U.S. Patent 3,567,763 and in German Patent 1,231,688 and reaction products of the aforementioned isocyanates with acetals as described in German Patent 1,072,385.
- Additional polyisocyanates suitable for use in this invention include those described by W. Siefken in Justus Liebigs Annalen der Chemie , 562, pp. 75-136, and in U.S. Patents 3,284,479; 4,089,835; 4,093,569; 4,221,876; 4,310,448; 4,359,550 and 4,495,309.
- Unsaturated isocyanates may also be used in the preparation of the unsaturated urethane component, as described above.
- "unsaturated isocyanate” means a compound containing at least one isocyanate group and at least one ethylenically unsaturated group capable of undergoing free radical initiated addition copolymerization with an unsaturated acid, acid salt, or anhydride such as, for example, methacrylic acid.
- These unsaturated isocyanates may be prepared by contacting a polyisocyanate with an ethylenically unsaturated alcohol, such as, for example, hydroxyethyl methacrylate, hydroxyethyl acrylate, and vinyl alcohol.
- the polyisocyanate used to prepare the unsaturated isocyanate has isocyanate groups of varying degrees of reactivity so that one isocyanate group may react preferentially with the ethylenically unsaturated alcohol, leaving other isocyanate groups free to react with additional active hydrogen-containing compounds.
- the primary isocyanate group of the isopherone diisocyanate will react with the ethylenically unsaturated alcohol to make the unsaturated isocyanate, leaving the tertiary isocyanate group free to react with additional active hydrogen-containing compounds in the preparation of the unsaturated urethane component.
- the polyisocyanate and ethylenically unsaturated alcohol are combined in amounts so that the ratio of isocyanate groups:active hydrogen groups is at least 1.5, more preferably at least 1.8, and most preferably at least 2.0; and is preferably no greater than 6.5, more preferably no greater than 5.0, and most preferably no greater than 3.5.
- Additional unsaturated isocyanates which may also be used include, for example, isocyanatoalkyl esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, ⁇ , ⁇ -ethylenically unsaturated isocyanates, monovinylidene aryl isocyanates, and monovinylidene arylmethyl isocyanates.
- isocyanates and methods for their preparation are described in U.S. Patents 4,390,645, 2,718,516, and 2,821,544, and British Patent No. 1,252,099.
- unsaturated isocyanates include, for example, 2-methyl-5-vinylbenzene-1,4-diisocyanate and 1-(alpha-isocyanato-alpha-methyl)ethyl-3(alpha-methyl) ethenyl benzene.
- An unsaturated hydroxy-functional reactant may be used in the preparation of the unsaturated urethane polymer.
- unsaturated hydroxy-functional reactants include unsaturated alcohols such as hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl propylacrylate, vinyl alcohol, glycerol mono allyl ether, glycerol methacrylate, N,N-dimethylol-1-butene, and polyols capped with an unsaturated isocyanate, as described in U.S. Patent 4,390,645.
- Active hydrogen-containing compounds suitable for use in the practice of this invention include any compound with a plurality of moieties containing a hydrogen atom which is active according to the Zerewitinoff test described by Kohler in the Journal of the American Chemical Society , Vol. 49, page 3181 (1927).
- Illustrative of such active hydrogen moieties are -COOH, -OH, -NH2, -NH-, -CONH2, -SH, and -CONH-.
- Typical active hydrogen-containing compounds include polyols, polyamines, polyamides, polymercaptans, and polyacids. Examples of such active hydrogen-containing compounds are described in U.S. Patents 4,390,645.
- the active hydrogen-containing compound preferably has an equivalent weight of at least 250 in order to provide good low temperature properties, and is more preferably at least 500, and most preferably at least 1,000; and is preferably no greater than 5,000, more preferably no greater than 3,000, and most preferably no greater than 2,000.
- the active hydrogen-containing compound has a functionality of 2 to 4 groups per molecule, more preferably of 2 to 3 groups per molecule, and most preferably 2 groups per molecule. Higher functionalities may cause excessive cross-linking, and result in an adhesive which is too viscous to handle and apply easily.
- the active hydrogen-containing compound is a polyether or polyester polyol.
- suitable polyester polyols include those which are the reaction product of a polyhydric alcohol and a polycarboxylic acid, acid anhydride, or acid chloride.
- Polyether polyols are more preferred for their low glass transition temperatures, and such polyols include polymers of alkylene oxides such as ethylene oxide, propylene oxide, tetrahydrofuran, or mixtures thereof, which are initiated with polyhydric materials such as water or polyhydric alcohols.
- the active hydrogen-containing compound is a poly(tetramethyleneoxy) polyol with an equivalent weight of at least 250, more preferably at least 500, and most preferably at least 1,000; and is preferably no greater than 5,000, more preferably no greater than 3,000, and most preferably no greater than 2,000.
- the unsaturated urethane may be prepared by several methods, using the reactants previously described.
- the reactants are preferably used in quantities such that the ratio of isocyanate groups:active hydrogen groups is at least 1.00:1.00, more preferably at least 1.00:1.02, and most preferably at least 1.00:1.05; and is preferably no greater than 1.00:1.40, more preferably no greater than 1.00:1.25, and most preferably no greater than 1.00:1.10.
- an excess over stoichiometry of isopherone diisocyanate may be reacted with hydroxyethyl methacrylate to form an unsaturated isocyanate, which may then be reacted with sufficient additional active hydrogen-containing compounds to react with all of the remaining isocyanate functionalities.
- the number of unsaturation sites in the unsaturated urethane is preferably in the range of at least 0.2 meq/g, more preferably at least 0.4 meq/g, and most preferably at least 0.6 meq/g; and is preferably no greater than 1.3 meq/g, more preferably no greater than 1.1 meq/g, and most preferably no greater than 0.9 meq/g.
- the unsaturated urethane is preferably prepared in the presence of a catalyst promoting the formation of urethane linkages, such as, for example, a stannous or stannic compound, such as a stannous salt of a carboxylic acid (e.g., stannous octoate, stannous oleate, stannous acetate, and stannous laurate), a trialkyltin oxide, a dialkytin dicarboxylate (e.g., dibutyltin dilaurate, dibutyltin diacetate, diethyltin diacetate, and dihexyltin diacetate), a dialkyltin dihalide, or a dialkyltin oxide, such as di-2-ethylhexyltin oxide or dioctyltin dioxide, a tertiary amine, or a tin mercaptide.
- Tertiary amine catalysts include trialkylamines (e.g., trimethylamine, triethylamine), heterocyclic amines, such as N-alkylmorpholines (e.g., N-methylmorpholine, N-ethylmorpholine, dimethyldiaminodiethyl ether, etc.), 1,4-dimethylpiperazine, triethylenediamine, etc., and aliphatic polyamines, such as N,N,N',N'-tetramethyl-1,3-butanediamine.
- trialkylamines e.g., trimethylamine, triethylamine
- heterocyclic amines such as N-alkylmorpholines (e.g., N-methylmorpholine, N-ethylmorpholine, dimethyldiaminodiethyl ether, etc.), 1,4-dimethylpiperazine, triethylenediamine, etc.
- aliphatic polyamines such as N,N
- the catalyst is dimethylbis[(1-oxododecyl)oxy]-stannane which is preferably present in an amount in the range of from 0.001 to 5 weight percent, based on the weight of the mixture to be catalyzed.
- the unsaturated urethane may be prepared in a two-step procedure by first reacting a polyisocyanate with varying degrees of reactivity with an ethylenically unsaturated alcohol to form an unsaturated isocyanate, and then reacting the unsaturated isocyanate with additional active hydrogen-containing compounds to form an unsaturated urethane in a second step.
- the use of a polyisocyanate with varying degrees of reactivity is preferred so that one isocyanate group may react preferentially with the ethylenically unsaturated alcohol, leaving other isocyanate groups free to react with additional active hydrogen-containing compounds.
- the polymerizable ethylenically unsaturated acid, acid salt, or acid anhydride (hereafter “unsaturated acid”) is an acid, acid salt, or acid anhydride containing at least one ethylenically unsaturated group capable of undergoing free radical initiated addition polymerization with an unsaturated urethane, and of forming a vinyl addition polymer by addition homopolymerization or copolymerization with at least one other monomer containing one or more internal or terminal polymerizable ethylenically unsaturated groups.
- this unsaturated acid when polymerized, increases the glass transition temperature of the adhesive and promotes adhesion to the material to be bonded.
- unsaturated acids include, for example, free acid, anhydride, and salt forms of methacrylic acid, cis-aconitic acid, trans-aconitic acid, acrylic acid, itaconic acid, 2-sulfoethyl methacrylate, 2-sulfoethyl acrylate, 3-sulfopropyl methacrylate, 3-sulfopropyl acrylate, ⁇ -carboxyl ethyl acrylate, ⁇ -carboxyl, ⁇ -methyl ethyl methacrylate, maleic anhydride, 2-methyacryloxyethyl phosphate, 3-methacryloxypropyl phosphate, p-styrene sulfonic acid, and maleic acid.
- methacrylic acid cis-aconitic acid, trans-aconitic acid, acrylic acid, itaconic acid
- 2-sulfoethyl methacrylate 2-sulfoethyl acryl
- the unsaturated acid is a free acid, anhydride, or salt form of methacrylic acid, cis-aconitic acid, trans-aconitic acid, acrylic acid, itaconic acid, 2-sulfoethyl methacrylate, 2-sulfoethyl acrylate, 3-sulfopropyl methacrylate, 3-sulfopropyl acrylate, ⁇ -carboxyl ethyl acrylate, ⁇ -carboxyl, ⁇ -methyl ethyl methacrylate, maleic anhydride, 2-methyacryloxyethyl phosphate, 3-methacryloxypropyl phosphate; and more preferably is a free acid, anhydride, or salt form of methacrylic acid or acrylic acid, and most preferably is methacrylic acid or acrylic acid.
- the unsaturated urethane and the unsaturated acid are preferably combined in a weight ratio of urethane:acid of at least 2:1, more preferably at least 4:1, and most preferably at least 5:1; and is preferably no greater than 200:1, more preferably no greater than 12:1, and most preferably no greater than 9:1.
- the adhesives of the invention also comprise unsaturated plasticizers containing at least one ethylenically unsaturated group capable of undergoing free radical initiated addition polymerization with an unsaturated urethane or unsaturated acid.
- plasticizers include, for example, hexanediol diacrylate, hexanediol dimethacrylate, diallyl phthalate, trimethylol propane, trimethacrylatetrimethylol propane triacrylate, 2-butane-1,4-diol diacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl propylacrylate, vinyl alcohol, glycerol mono allyl ether, glycerol methacrylate, N,N-dimethylol-1-butene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate,
- the unsaturated plasticizer contains at least two ethylenically unsaturated groups to provide additional cross-linking capability under vinyl addition polymerization conditions, and is more preferably diallyl phthalate, hexanediol diacrylate, or hexanediol dimethacrylate.
- Such unsaturated plasticizers are especially useful in formulations for the bonding of sheet molding compounds, as they advantageously increase the cross-linking of the adhesive, reduce the viscosity of the uncured adhesive and promote adhesion to the substrate due to their polarity.
- Such plasticizers are preferably present in an amount of at least 5 percent, more preferably at least 10 percent, and most preferably at least 15 percent: and is preferably no greater than 25 percent, more preferably no greater than 20 percent, by weight of the adhesive.
- the adhesives of the invention also preferably include a free radical vinyl polymerization initiator, in an amount of at least 0.5 percent, more preferably at least 1.0 percent, and most preferably at least 2.0 percent; and is preferably no greater than 15.0 percent, more preferably no greater than 8.0 percent, and most preferably no greater than 4.0 percent by weight of the adhesive.
- This initiator is preferably added to the adhesive when the unsaturated urethane and the unsaturated monomer are combined, and will allow the adhesive to cure at elevated temperatures.
- initiators include, for example, t-amyl perbenzoate, and peroxides such as hydrogen peroxide, diacyl peroxides, ketone peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, hydroperoxides, peroxyketals, tert-butyl hydroperoxide, tert butyl peroctoate, and similar percarboxylic acid esters, and azobisisobutyronitrile.
- peroxides such as hydrogen peroxide, diacyl peroxides, ketone peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, hydroperoxides, peroxyketals, tert-butyl hydroperoxide, tert butyl peroctoate, and similar percarboxylic acid esters, and azobisisobutyronitrile.
- the adhesives of the invention also preferably contain materials which stabilize the unsaturated acid at storage temperatures.
- materials include, for example, talc or surface-treated clay, which preferably has a pH of from 7.0 to 10.0, and more preferably from 9.0 to 10.0, and which is preferably present in a weight ratio of talc or surface-treated clay: unsaturated acid of from 1:1 to 20:1.
- the adhesive also preferably contains inhibitors, or free radical scavengers, which inhibit the polymerization of the unsaturated urethane and the unsaturated acid at storage temperatures. Examples of such inhibitors include p-benzoquinone and hydroquinone and derivatives thereof, which are preferably present in an amount of from 0.01 to 1.5 weight percent of the adhesive.
- the adhesives of the invention may also be compounded with fillers and additives to modify rheological properties such as viscosity, sag resistance, and flow rate.
- fillers and additives include, for example, carbon black, surface-treated fumed silicas, titanium dioxide, calcium carbonate, talc, defoaming agents, mica, aluminum oxide, clays, and glass phenolic, or aluminum oxide bubbles.
- a surface-treated fumed silica is used, it is preferably used in an amount of from 1.0 weight percent to 10.0 weight percent, based on the weight of the unsaturated urethane and unsaturated acid, together.
- Other additives which are suitable for use in the preparation of the adhesive of the invention include ultraviolet stabilizers and anti-oxidants.
- the adhesives of the invention also preferably contains one or more saturated plasticizers to modify the rheological properties of the adhesive.
- Suitable plasticizers include, for example, 2-ethylhexyl diphenyl phosphate, o-phthalates, adipates, adipic acid, benzoic acid, glycols, phosphoric acid, phthalic acid, and sebacic acid, which are preferably used in an amount of from 1 to 20 weight percent, based on the weight of the adhesive.
- the saturated plasticizer will advantageously control the shrinkage of the adhesive upon curing.
- the composite of the invention may be prepared by bonding a fiberglass-reinforced polyester substrate to a second substrate by means of a cured layer of adhesive, wherein the adhesive comprises
- Adhesive A - A 328-lb portion of the above mixture is compounded under reduced pressure with 152 g of parabenzoquinone, 41 lb of methacrylic acid and 48 lb of 2-ethylhexyl diphenyl phosphate for 30 minutes. Fumed silica (41 lb) is then added and mixed for 15 minutes. Talc (195 lb) with a pH in the range of from 9 to 10 is then added and mixed for 15 minutes, and 18.56 lb of LupersolTM TAEC free radical initiator added to the mixture and mixed for 30 minutes.
- Adhesive B - A 500-lb portion of the above unsaturated urethane is compounded under reduced pressure with 232 g of parabenzoquinone, 62 lb of methacrylic acid and 73 lb of 2-ethylhexyl diphenyl phosphate for 30 minutes. Fumed silica (62 lb) is then added and mixed for 15 minutes. Talc (297 lb) with a pH in the range of from 9-10 is then added and mixed for 15 minutes, and 28.24 lb of LupersolTM TAEC free radical initiator added to the mixture and mixed for 30 minutes.
- adhesives are prepared as in Example 1A using ratios of components shown in Table I.
- the adhesive samples were tested bonding samples of GenCorp's DiversitechTM 7113 sheet molding compound (SMC) together.
- SMC samples were bonded with a 30 mil thickness of adhesive, cured for 1 hour at 250°F, cooled for 2 hours at room temperature, and heated at 180°F for 30 min. before testing.
- the samples were lap shear tested with a 2000 lb. load cell at a speed of 0.5 in/min.
- a 720.4 portion of the above mixture is compounded under reduced pressure with 134.0 g of diallyl phthalate, 75.3 g of hexanediol dimethacrylate, 108.9 g of methacrylic acid and 108.9 g of 2-ethylhexyl diphenyl phosphate for 30 minutes. Fumed silica (125.6 g) is then added and mixed for 15 minutes. Talc (502.2 g) with a pH in the range of from 9 to 10 is then added and mixed for 15 minutes, and 41.9 g t-amyl perbenzoate (free radical initiator) is added to the mixture and mixed for 30 minutes.
Abstract
Disclosed herein is a one-part adhesive which comprises a mixture of: (a) a polymerizable ethylenically unsaturated urethane polymer; and(b) a polymerizable ethylenically unsaturated acid, acid salt, or acid anhydride wherein component (b) is present in an amount in the range of from 0.5 to 50 weight percent of component (a). Such an adhesive is especially suitable for bonding components together in the manufacture of automobiles, and is particularly suitable for bonding sheet molding compound (SMC) components to metal or to other SMC components.
Description
- This invention relates to structural acrylic urethane adhesives. Such adhesives are useful for bonding materials together in the assembly of automobiles. More specifically, this invention relates to an adhesive suitable for bonding fiberglass-reinforced polyester substrates.
- Transparent adhesives for glass which comprise urethane acrylates in acylic acid diluents, and which are suitable for the production of clear glass laminates are known and are described, for example, in U.S. Patent 4,717,739. However, such adhesives are not well suited for bonding fiberglass-reinforced polyester substrates, such as are useful, for example, in the manufacture of vehicles, particularly automobiles. It would be desireable to provide a heat-cureable one-part adhesive for bonding fiberglass-reinforced polyester substrates (also referred to as sheet molding compound (SMC) components) to each other or to a metal substrate, which would provide sufficient lap shear strength over a sufficient range of temperatures to be useful in the manufacture of vehicles.
- In one aspect, this invention is a one-part adhesive which comprises a mixture of:
- (a) a polymerizable ethylenically unsaturated urethane polymer; and
- (b) a polymerizable ethylenically unsaturated acid, acid salt, or acid anhydride
- In a second aspect, this invention is a one-part adhesive which comprises a mixture of:
- (a) a polymerizable ethylenically unsaturated urethane polymer; and
- (b) a polymerizable ethylenically unsaturated acid, acid salt, or acid anhydride
- In a third aspect, this invention is a composite comprising a fiberglass-reinforced polyester substrate bonded to a second substrate, by means of a cured layer of a one-part adhesive between said substrates comprising a mixture of
- (a) a polymerizable ethylenically unsaturated urethane polymer; and
- (b) a polymerizable ethylenically unsaturated acid, acid salt, or acid anhydride
- The adhesives of the invention, and the adhesive used in the composite of the invention are one-part adhesives which advantageously has high strength characteristics when used to bond fiberglass-reinforced polyester substrates without the use of a primer. In addition, the cured adhesives of this invention have a wide-ranging glass transition temperature which make them suitable for high and low temperature applications.
- The adhesives of the invention are thixotropic, heat-curable mixtures which, when cured, are graft copolymers of a urethane and vinyl polymers, wherein the vinyl portion contains pendant acid groups. The copolymer is prepared by copolymerizing an ethylenically unsaturated urethane polymer with an ethylenically unsaturated acid, acid salt, or anhydride. The mixture is preferably prepared with inhibitors which prevent the mixture from copolymerizing before application.
- According to the invention, the polymerizable ethylenically unsaturated urethane polymer component (hereafter "unsaturated urethane") of the adhesive is a urethane polymer which has at least one unsaturation site which will copolymerize with the unsaturated acid, acid salt, or anhydride component. The unsaturated urethane preferably has a molecular weight of at least 1,000, more preferably at least 2,000, and most preferably at least 4,000; and is preferably no greater than 35,000, more preferably no greater than 15,000, and most preferably no greater than 10,000.
- The unsaturated urethane may be prepared by a variety of methods. For example, this component may be prepared by contacting a polyisocyanate with an unsaturated hydroxy-functional reactant, optionally in the presence of additional active hydrogen-containing compounds and/or additional polyisocyanates. As another example, this component may also be prepared by contacting an unsaturated isocyanate with a hydroxy-functional reactant, optionally in the presence of additional active hydrogen-containing compounds and/or additional polyisocyanates.
- Isocyanates which are suitable for use in the preparation of the unsaturated urethane component include aromatic, aliphatic, cycloaliphatic, araliphatic, and heterocyclic polyisocyanates, and mixtures thereof, with alicyclic isocyanates as the most preferred for their stability in light. Preferably, the isocyanate has a functionality of 2 to 4 isocyanate groups per molecule, more preferably of 2 to 3 isocyanate groups per molecule, and most preferably 2 isocyanate groups per molecule. Higher functionalities may also be used, but may cause excessive cross-linking, and result in an adhesive which is too viscous to handle and apply easily, and can cause the cured adhesive to be too brittle. Specific examples of isocyanates include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-and 1,4-diisocyanate and mixtures of these isomers; 1-isocyanato-3,3,5-trimethyl-5-isocyanato methyl cyclohexane (see e.g., German Auslegeschrift No. 1,202,785); 2,4- and 2,6-hexahydrotolylene diisocyanate and mixtures of these isomers, hexahydro-1,3- and/or 1,4-phenylene diisocyanate, perhydro-2,5'- and/or 4,4'-diphenyl methane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and mixtures of these isomers, diphenyl methane-2,4'- and/or 4,4'-diisocyanate, naphthylene-1,5-diisocyanate, triphenyl methane-4,4',4"-triisocyanate, polyphenyl polymethylene polyisocyanates of the type obtained by condensing aniline with formaldehyde, followed by phosgenation and such as described for example in British Patents 874,430 and 848,671, perchlorinated aryl polyisocyanates of the type described in German Auslegeschrift 1,157,601, polyisocyanates containing carbodiimide groups of the type described in German Patent 1,092,007, diisocyanates of the type described in U.S. Patent 3,492,330, polyisocyanates containing allophanate groups of the type described, for example, in British Patent 994,890, in Belgian Patent 761,626 and in published Dutch Patent Application No. 7,102,524, polyisocyanates containing isocyanurate groups of the type described in German Patents 1,022,789; 1,222,067 and 1,027,394 and in German Offenlegungsschrift 1,929,034 and 2,004,048, polyisocyanates containing urethane groups of the type described, for example, in Belgian Patent 752,261 or in U.S. Patent 3,394,164, polyisocyanates containing acrylated urea groups as described in German Patent 1,230,778, polyisocyanates containing biuret groups of the type described, for example, in German Patent 1,101,392, in British Patent 889,050 and in French Patent 7,017,514, polyisocyanates obtained by telomerization reactions of the type described, for example, in Belgian Patent 723,640, polyisocyanates containing ester groups of the type described, for example, in British Patents 965,474 and 1,072,956, in U.S. Patent 3,567,763 and in German Patent 1,231,688 and reaction products of the aforementioned isocyanates with acetals as described in German Patent 1,072,385.
- Additional polyisocyanates suitable for use in this invention include those described by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pp. 75-136, and in U.S. Patents 3,284,479; 4,089,835; 4,093,569; 4,221,876; 4,310,448; 4,359,550 and 4,495,309.
- Unsaturated isocyanates may also be used in the preparation of the unsaturated urethane component, as described above. As used herein, "unsaturated isocyanate" means a compound containing at least one isocyanate group and at least one ethylenically unsaturated group capable of undergoing free radical initiated addition copolymerization with an unsaturated acid, acid salt, or anhydride such as, for example, methacrylic acid. These unsaturated isocyanates may be prepared by contacting a polyisocyanate with an ethylenically unsaturated alcohol, such as, for example, hydroxyethyl methacrylate, hydroxyethyl acrylate, and vinyl alcohol.
- Preferably, the polyisocyanate used to prepare the unsaturated isocyanate has isocyanate groups of varying degrees of reactivity so that one isocyanate group may react preferentially with the ethylenically unsaturated alcohol, leaving other isocyanate groups free to react with additional active hydrogen-containing compounds. For example, if an excess over stoichiometry of isopherone diisocyanate is used to prepare the unsaturated isocyanate, the primary isocyanate group of the isopherone diisocyanate will react with the ethylenically unsaturated alcohol to make the unsaturated isocyanate, leaving the tertiary isocyanate group free to react with additional active hydrogen-containing compounds in the preparation of the unsaturated urethane component. In the preparation of such an unsaturated isocyanate, the polyisocyanate and ethylenically unsaturated alcohol are combined in amounts so that the ratio of isocyanate groups:active hydrogen groups is at least 1.5, more preferably at least 1.8, and most preferably at least 2.0; and is preferably no greater than 6.5, more preferably no greater than 5.0, and most preferably no greater than 3.5.
- Additional unsaturated isocyanates which may also be used include, for example, isocyanatoalkyl esters of α,β-ethylenically unsaturated carboxylic acids, α,β-ethylenically unsaturated isocyanates, monovinylidene aryl isocyanates, and monovinylidene arylmethyl isocyanates. Such isocyanates and methods for their preparation are described in U.S. Patents 4,390,645, 2,718,516, and 2,821,544, and British Patent No. 1,252,099. Other unsaturated isocyanates include, for example, 2-methyl-5-vinylbenzene-1,4-diisocyanate and 1-(alpha-isocyanato-alpha-methyl)ethyl-3(alpha-methyl) ethenyl benzene.
- An unsaturated hydroxy-functional reactant may be used in the preparation of the unsaturated urethane polymer. Examples of such unsaturated hydroxy-functional reactants include unsaturated alcohols such as hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl propylacrylate, vinyl alcohol, glycerol mono allyl ether, glycerol methacrylate, N,N-dimethylol-1-butene, and polyols capped with an unsaturated isocyanate, as described in U.S. Patent 4,390,645.
- Active hydrogen-containing compounds suitable for use in the practice of this invention include any compound with a plurality of moieties containing a hydrogen atom which is active according to the Zerewitinoff test described by Kohler in the Journal of the American Chemical Society, Vol. 49, page 3181 (1927). Illustrative of such active hydrogen moieties are -COOH, -OH, -NH₂, -NH-, -CONH₂, -SH, and -CONH-. Typical active hydrogen-containing compounds include polyols, polyamines, polyamides, polymercaptans, and polyacids. Examples of such active hydrogen-containing compounds are described in U.S. Patents 4,390,645. The active hydrogen-containing compound preferably has an equivalent weight of at least 250 in order to provide good low temperature properties, and is more preferably at least 500, and most preferably at least 1,000; and is preferably no greater than 5,000, more preferably no greater than 3,000, and most preferably no greater than 2,000. Preferably, the active hydrogen-containing compound has a functionality of 2 to 4 groups per molecule, more preferably of 2 to 3 groups per molecule, and most preferably 2 groups per molecule. Higher functionalities may cause excessive cross-linking, and result in an adhesive which is too viscous to handle and apply easily.
- Preferably, the active hydrogen-containing compound is a polyether or polyester polyol. Examples of suitable polyester polyols include those which are the reaction product of a polyhydric alcohol and a polycarboxylic acid, acid anhydride, or acid chloride. Polyether polyols are more preferred for their low glass transition temperatures, and such polyols include polymers of alkylene oxides such as ethylene oxide, propylene oxide, tetrahydrofuran, or mixtures thereof, which are initiated with polyhydric materials such as water or polyhydric alcohols. Most preferably, the active hydrogen-containing compound is a poly(tetramethyleneoxy) polyol with an equivalent weight of at least 250, more preferably at least 500, and most preferably at least 1,000; and is preferably no greater than 5,000, more preferably no greater than 3,000, and most preferably no greater than 2,000.
- As described above, the unsaturated urethane may be prepared by several methods, using the reactants previously described. In the preparation of the unsaturated urethane, the reactants are preferably used in quantities such that the ratio of isocyanate groups:active hydrogen groups is at least 1.00:1.00, more preferably at least 1.00:1.02, and most preferably at least 1.00:1.05; and is preferably no greater than 1.00:1.40, more preferably no greater than 1.00:1.25, and most preferably no greater than 1.00:1.10. For example, an excess over stoichiometry of isopherone diisocyanate may be reacted with hydroxyethyl methacrylate to form an unsaturated isocyanate, which may then be reacted with sufficient additional active hydrogen-containing compounds to react with all of the remaining isocyanate functionalities. The number of unsaturation sites in the unsaturated urethane is preferably in the range of at least 0.2 meq/g, more preferably at least 0.4 meq/g, and most preferably at least 0.6 meq/g; and is preferably no greater than 1.3 meq/g, more preferably no greater than 1.1 meq/g, and most preferably no greater than 0.9 meq/g.
- The unsaturated urethane is preferably prepared in the presence of a catalyst promoting the formation of urethane linkages, such as, for example, a stannous or stannic compound, such as a stannous salt of a carboxylic acid (e.g., stannous octoate, stannous oleate, stannous acetate, and stannous laurate), a trialkyltin oxide, a dialkytin dicarboxylate (e.g., dibutyltin dilaurate, dibutyltin diacetate, diethyltin diacetate, and dihexyltin diacetate), a dialkyltin dihalide, or a dialkyltin oxide, such as di-2-ethylhexyltin oxide or dioctyltin dioxide, a tertiary amine, or a tin mercaptide. Tertiary amine catalysts include trialkylamines (e.g., trimethylamine, triethylamine), heterocyclic amines, such as N-alkylmorpholines (e.g., N-methylmorpholine, N-ethylmorpholine, dimethyldiaminodiethyl ether, etc.), 1,4-dimethylpiperazine, triethylenediamine, etc., and aliphatic polyamines, such as N,N,N',N'-tetramethyl-1,3-butanediamine. Preferably, the catalyst is dimethylbis[(1-oxododecyl)oxy]-stannane which is preferably present in an amount in the range of from 0.001 to 5 weight percent, based on the weight of the mixture to be catalyzed.
- As mentioned above, the unsaturated urethane may be prepared in a two-step procedure by first reacting a polyisocyanate with varying degrees of reactivity with an ethylenically unsaturated alcohol to form an unsaturated isocyanate, and then reacting the unsaturated isocyanate with additional active hydrogen-containing compounds to form an unsaturated urethane in a second step. The use of a polyisocyanate with varying degrees of reactivity is preferred so that one isocyanate group may react preferentially with the ethylenically unsaturated alcohol, leaving other isocyanate groups free to react with additional active hydrogen-containing compounds. When this procedure is followed, it is preferable to add urethane catalyst in small amounts in each step, in order to prevent all of the isocyanate groups in the polyisocyanate from reacting with the unsaturated alcohol in the first step.
- The polymerizable ethylenically unsaturated acid, acid salt, or acid anhydride (hereafter "unsaturated acid") is an acid, acid salt, or acid anhydride containing at least one ethylenically unsaturated group capable of undergoing free radical initiated addition polymerization with an unsaturated urethane, and of forming a vinyl addition polymer by addition homopolymerization or copolymerization with at least one other monomer containing one or more internal or terminal polymerizable ethylenically unsaturated groups. Advantageously, this unsaturated acid, when polymerized, increases the glass transition temperature of the adhesive and promotes adhesion to the material to be bonded.
- Examples of such unsaturated acids include, for example, free acid, anhydride, and salt forms of methacrylic acid, cis-aconitic acid, trans-aconitic acid, acrylic acid, itaconic acid, 2-sulfoethyl methacrylate, 2-sulfoethyl acrylate, 3-sulfopropyl methacrylate, 3-sulfopropyl acrylate, β-carboxyl ethyl acrylate, β-carboxyl, β-methyl ethyl methacrylate, maleic anhydride, 2-methyacryloxyethyl phosphate, 3-methacryloxypropyl phosphate, p-styrene sulfonic acid, and maleic acid. Preferably, the unsaturated acid is a free acid, anhydride, or salt form of methacrylic acid, cis-aconitic acid, trans-aconitic acid, acrylic acid, itaconic acid, 2-sulfoethyl methacrylate, 2-sulfoethyl acrylate, 3-sulfopropyl methacrylate, 3-sulfopropyl acrylate, β-carboxyl ethyl acrylate, β-carboxyl, β-methyl ethyl methacrylate, maleic anhydride, 2-methyacryloxyethyl phosphate, 3-methacryloxypropyl phosphate; and more preferably is a free acid, anhydride, or salt form of methacrylic acid or acrylic acid, and most preferably is methacrylic acid or acrylic acid.
- The unsaturated urethane and the unsaturated acid are preferably combined in a weight ratio of urethane:acid of at least 2:1, more preferably at least 4:1, and most preferably at least 5:1; and is preferably no greater than 200:1, more preferably no greater than 12:1, and most preferably no greater than 9:1.
- In another preferred embodiment, the adhesives of the invention also comprise unsaturated plasticizers containing at least one ethylenically unsaturated group capable of undergoing free radical initiated addition polymerization with an unsaturated urethane or unsaturated acid. Examples of such plasticizers include, for example, hexanediol diacrylate, hexanediol dimethacrylate, diallyl phthalate, trimethylol propane, trimethacrylatetrimethylol propane triacrylate, 2-butane-1,4-diol diacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl propylacrylate, vinyl alcohol, glycerol mono allyl ether, glycerol methacrylate, N,N-dimethylol-1-butene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, hexyl acrylate, 2-ethylhexyl acrylate, laurel acrylate, laurel methacrylate, diethylene glycol methacrylate, dicyclopentadienyloxyethyl methacrylate, tetrahydrofurfuryl methacrylate, and glycidyl methacrylate. Preferably, the unsaturated plasticizer contains at least two ethylenically unsaturated groups to provide additional cross-linking capability under vinyl addition polymerization conditions, and is more preferably diallyl phthalate, hexanediol diacrylate, or hexanediol dimethacrylate. Such unsaturated plasticizers are especially useful in formulations for the bonding of sheet molding compounds, as they advantageously increase the cross-linking of the adhesive, reduce the viscosity of the uncured adhesive and promote adhesion to the substrate due to their polarity. Such plasticizers are preferably present in an amount of at least 5 percent, more preferably at least 10 percent, and most preferably at least 15 percent: and is preferably no greater than 25 percent, more preferably no greater than 20 percent, by weight of the adhesive.
- The adhesives of the invention also preferably include a free radical vinyl polymerization initiator, in an amount of at least 0.5 percent, more preferably at least 1.0 percent, and most preferably at least 2.0 percent; and is preferably no greater than 15.0 percent, more preferably no greater than 8.0 percent, and most preferably no greater than 4.0 percent by weight of the adhesive. This initiator is preferably added to the adhesive when the unsaturated urethane and the unsaturated monomer are combined, and will allow the adhesive to cure at elevated temperatures. Examples of such initiators include, for example, t-amyl perbenzoate, and peroxides such as hydrogen peroxide, diacyl peroxides, ketone peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, hydroperoxides, peroxyketals, tert-butyl hydroperoxide, tert butyl peroctoate, and similar percarboxylic acid esters, and azobisisobutyronitrile.
- The adhesives of the invention also preferably contain materials which stabilize the unsaturated acid at storage temperatures. Such materials include, for example, talc or surface-treated clay, which preferably has a pH of from 7.0 to 10.0, and more preferably from 9.0 to 10.0, and which is preferably present in a weight ratio of talc or surface-treated clay: unsaturated acid of from 1:1 to 20:1. The adhesive also preferably contains inhibitors, or free radical scavengers, which inhibit the polymerization of the unsaturated urethane and the unsaturated acid at storage temperatures. Examples of such inhibitors include p-benzoquinone and hydroquinone and derivatives thereof, which are preferably present in an amount of from 0.01 to 1.5 weight percent of the adhesive.
- The adhesives of the invention may also be compounded with fillers and additives to modify rheological properties such as viscosity, sag resistance, and flow rate. Such materials include, for example, carbon black, surface-treated fumed silicas, titanium dioxide, calcium carbonate, talc, defoaming agents, mica, aluminum oxide, clays, and glass phenolic, or aluminum oxide bubbles. When a surface-treated fumed silica is used, it is preferably used in an amount of from 1.0 weight percent to 10.0 weight percent, based on the weight of the unsaturated urethane and unsaturated acid, together. Other additives which are suitable for use in the preparation of the adhesive of the invention include ultraviolet stabilizers and anti-oxidants.
- The adhesives of the invention also preferably contains one or more saturated plasticizers to modify the rheological properties of the adhesive. Suitable plasticizers include, for example, 2-ethylhexyl diphenyl phosphate, o-phthalates, adipates, adipic acid, benzoic acid, glycols, phosphoric acid, phthalic acid, and sebacic acid, which are preferably used in an amount of from 1 to 20 weight percent, based on the weight of the adhesive. The saturated plasticizer will advantageously control the shrinkage of the adhesive upon curing.
- The composite of the invention may be prepared by bonding a fiberglass-reinforced polyester substrate to a second substrate by means of a cured layer of adhesive, wherein the adhesive comprises
- (a)a polymerizable ethylenically unsaturated urethane polymer; and
- (b) a polymerizable ethylenically unsaturated acid, acid salt, or acid anhydride
- The following examples are given to illustrate the invention and should not be interpreted as limiting it in any way. Unless stated otherwise, all parts and percentages are given by weight.
- To a reactor is added 123 lb of isopherone diisocyanate, 15 g hydroquinone, and 7.02 g of a tin urethane catalyst. These components are mixed while 43 lb of 2-hydroxy methacrylate is added slowly to the reactor at a temperature of less than 50°C. A poly(tetramethyleneoxy) polyol (384 lb) with a molecular weight of 1000 is then added to the reactor at a temperature of less than 70°C and the components are mixed for one hour. The reaction is carried out at these temperatures to help prevent the unsaturated reactants from polymerizing. To this mixture is then added 20.25 g of a tin urethane catalyst, and the components are further mixed until substantially all of the isocyanate groups present have reacted. Diallyl phthalate (197 lb) is then combined with the mixture.
- Adhesive A - A 328-lb portion of the above mixture is compounded under reduced pressure with 152 g of parabenzoquinone, 41 lb of methacrylic acid and 48 lb of 2-ethylhexyl diphenyl phosphate for 30 minutes. Fumed silica (41 lb) is then added and mixed for 15 minutes. Talc (195 lb) with a pH in the range of from 9 to 10 is then added and mixed for 15 minutes, and 18.56 lb of Lupersol™ TAEC free radical initiator added to the mixture and mixed for 30 minutes.
- Adhesive B - A 500-lb portion of the above unsaturated urethane is compounded under reduced pressure with 232 g of parabenzoquinone, 62 lb of methacrylic acid and 73 lb of 2-ethylhexyl diphenyl phosphate for 30 minutes. Fumed silica (62 lb) is then added and mixed for 15 minutes. Talc (297 lb) with a pH in the range of from 9-10 is then added and mixed for 15 minutes, and 28.24 lb of Lupersol™ TAEC free radical initiator added to the mixture and mixed for 30 minutes.
- Using samples of unsaturated urethane prepared as above, adhesives are prepared as in Example 1A using ratios of components shown in Table I. The adhesive samples were tested bonding samples of GenCorp's Diversitech™ 7113 sheet molding compound (SMC) together. The SMC samples were bonded with a 30 mil thickness of adhesive, cured for 1 hour at 250°F, cooled for 2 hours at room temperature, and heated at 180°F for 30 min. before testing. The samples were lap shear tested with a 2000 lb. load cell at a speed of 0.5 in/min.
- To a reactor is added 23.127 lb of isopherone diisocyanate, 0.008 lb hydroquinone, and 0.003 lb of a tin urethane catalyst. These components are mixed while 12.188 lb of 2-hydroxy methacrylate is added slowly to the reactor. A poly(tetramethyleneoxy) polyol (64.667 lb) with a molecular weight of 1000 is then added to the reactor and the components are mixed for one hour. To this mixture is then added 0.007 lb of a tin urethane catalyst, and the components are further mixed until substantially all of the isocyanate groups present have reacted.
-
- To a reactor is added 990 g of isopherone diisocyanate, 0.22 g hydroquinone, and 0.12 g of a tin urethane catalyst. These components are mixed while 310 g of 2-hydroxyethyl acrylate is added slowly to the reactor. A poly(tetramethyleneoxy) polyol (3004 g) with a molecular weight of 1000 is then added to the reactor and the components are mixed for one hour. To this mixture is then added 0.14 g of a tin urethane catalyst and 1079 g of diallyl phthalate, and the components are further mixed until substantially all of the isocyanate groups present have reacted.
-
- To a reactor is added 761.2 g of isopherone diisocyanate, 0.22 g hydroquinone, and 0.1 g of a tin urethane catalyst. These components are mixed while 250 g of 2-hydroxyethyl methacrylate is added slowly to the reactor. A poly(tetramethyleneoxy) polyol (2086 g) with a molecular weight of 1000 is then added to the reactor and the components are mixed for one hour. To this mixture is then added 0.14 g of a tin urethane catalyst and 788 g of diallyl phthalate, and the components are further mixed until substantially all of the isocyanate groups present have reacted.
-
- To a reactor is added 747.1 g of isopherone diisocyanate, 7.0 g p-benzoquinone, and 0.1 g of a tin urethane catalyst. These components are mixed while 350 g of 2-hydroxyethyl methacrylate is added slowly to the reactor at a temperature of less than 50°C. A poly(tetramethyleneoxy) polyol (2109.7 g) with a molecular weight of 1000 is then added to the reactor at a temperature of less than 70°C and the components are mixed for one hour. To this mixture is then added 0.26 g of a tin urethane catalyst, and the components are further mixed until substantially all of the isocyanate groups present have reacted. Diallyl phthalate (197 lb) is then combined with the mixture.
- A 720.4 portion of the above mixture is compounded under reduced pressure with 134.0 g of diallyl phthalate, 75.3 g of hexanediol dimethacrylate, 108.9 g of methacrylic acid and 108.9 g of 2-ethylhexyl diphenyl phosphate for 30 minutes. Fumed silica (125.6 g) is then added and mixed for 15 minutes. Talc (502.2 g) with a pH in the range of from 9 to 10 is then added and mixed for 15 minutes, and 41.9 g t-amyl perbenzoate (free radical initiator) is added to the mixture and mixed for 30 minutes.
-
wherein component (b) is present in an amount in the range of from 0.5 to 50 weight percent of component (a), and (c) an ethylenically unsaturated plasticizer containing at least two ethylenically unsaturated groups capable of undergoing free radical initiated addition polymerization with component (a) or (b).
wherein component (b) is present in an amount in the range of from 0.5 to 50 weight percent of component (a), and (c) talc or surface-treated clay with a pH in the range of from 7.0 to 10.0.
wherein component (b) is present in an amount in the range of 0.5 to 50 weight percent of component (a).
wherein component (b) is present in an amount in the range of 0.5 to 50 weight percent of component (a). Preferably, the adhesive is first applied to the fiberglass-reinforced polyester substrate, which is then applied to the second substrate before the adhesive reaches a tack-free state, and then cured. The second substrate may comprise any substrate which will adhere to the first substarte by means of the adhesive, but is preferably a metal or a fiberglass-reinforced polyester substrate. The adhesive may be prepared by any of the methods described above for preparation of the adhesives of the invention.
Claims (10)
- A one-part adhesive which comprises a mixture of:(a) a polymerizable ethylenically unsaturated urethane polymer; and(b) a polymerizable ethylenically unsaturated acid, acid salt, or acid anhydridewherein component (b) is present in an amount in the range of from 0.5 to 50 weight percent of component (a), and (c) an ethylenically unsaturated plasticizer containing at least two ethylenically unsaturated groups capable of undergoing free radical initiated addition polymerization with component (a) or (b).
- The adhesive of Claim 1 wherein component (a) comprises isopherone diisocyanate.
- The adhesive of Claim 1 wherein the ethylenically unsaturated plasticizer comprises diallyl phthalate.
- The adhesive of Claim 1 wherein the ethylenically unsaturated plasticizer comprises hexanediol dimethacrylate.
- A one-part adhesive which comprises a mixture of:(a) a polymerizable ethylenically unsaturated urethane polymer; and(b) a polymerizable ethylenically unsaturated acid, acid salt, or acid anhydridewherein component (b) is present in an amount in the range of from 0.5 to 50 weight percent of component (a), and (c) talc or surface-treated clay with a pH in the range of from 7.0 to 10.0.
- The adhesive of Claim 5 wherein the talc or surface-treated clay is present in an amount such that the weight ratio of talc or surface-treated clay:unsaturated acid is in the range of from 1:1 to 20:1.
- The adhesive of Claim 5 which additionally comprises a fumed silica, which is present in an amount of from 1.0 to 10.0 weight percent, based on the weight of components (a) and (b) together.
- A composite comprising a fiberglass-reinforced polyester substrate bonded to a second substrate, by means of a cured layer of a one-part adhesive between said substrates comprising a mixture of(a) a polymerizable ethylenically unsaturated urethane polymer; and(b) a polymerizable ethylenically unsaturated acid, acid salt, or acid anhydridewherein component (b) is present in an amount in the range of from 0.5 to 50 weight percent of component (a).
- The composite of Claim 8 wherein the adhesive additionally comprises (c) talc or surface-treated clay with a pH in the range of from 7.0 to 10.0.
- The composite of Claim 8 wherein the adhesive additionally comprises (c) an ethylenically unsaturated plasticizer containing at least two ethylenically unsaturated groups capable of undergoing free radical initiated addition polymerization with component (a) or (b).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US464828 | 1990-01-16 | ||
US07/464,828 US5063269A (en) | 1990-01-16 | 1990-01-16 | One-part primerless adhesive |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0439040A1 true EP0439040A1 (en) | 1991-07-31 |
Family
ID=23845402
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91100367A Withdrawn EP0439040A1 (en) | 1990-01-16 | 1991-01-14 | One-part primerless adhesive |
Country Status (5)
Country | Link |
---|---|
US (1) | US5063269A (en) |
EP (1) | EP0439040A1 (en) |
AU (1) | AU628769B2 (en) |
CA (1) | CA2034166C (en) |
ZA (1) | ZA91293B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0591803A1 (en) * | 1992-10-05 | 1994-04-13 | BASF Aktiengesellschaft | Cartridge for chemical fixing engineering |
WO1999033930A1 (en) * | 1997-12-24 | 1999-07-08 | Essex Specialty Products, Inc. | Primerless adhesive for a painted surface |
US6355317B1 (en) | 1997-06-19 | 2002-03-12 | H. B. Fuller Licensing & Financing, Inc. | Thermoplastic moisture cure polyurethanes |
EP1426390A2 (en) * | 2002-11-14 | 2004-06-09 | Rohm And Haas Company | Curable clay composition: composition, processes, and uses thereof |
Families Citing this family (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2687499B1 (en) * | 1992-02-13 | 1994-04-15 | Elf Atochem Sa | PROCESS FOR THE CONDITIONING OF ION EXCHANGE RESINS CONTAMINATED BY RADIOACTIVE ELEMENTS. |
JPH07506148A (en) * | 1993-02-12 | 1995-07-06 | エセックス スペシャリティ プロダクツ,インコーポレイティド | Heat-activated modular components, their use and methods for direct glass fitting to vehicles, and adhesives |
US5356529A (en) * | 1993-05-03 | 1994-10-18 | Ppg Industries, Inc. | Electrodepositable compositions containing triorganotin catalysts |
US5718817A (en) * | 1993-07-28 | 1998-02-17 | Elf Atochem North America, Inc. | Catalyst for low temperature cure of blocked isocyanates |
US6001204A (en) * | 1994-10-11 | 1999-12-14 | Essex Speciality Products, Inc. | Heat activatable modular structural member, its use and process for the direct glazing of vehicles and adhesive therefor |
US5852137A (en) * | 1997-01-29 | 1998-12-22 | Essex Specialty Products | Polyurethane sealant compositions |
JP2002508431A (en) * | 1997-12-18 | 2002-03-19 | エセックス スペシャリティ プロダクツ,インコーポレイティド | Method for improving adhesion of urethane adhesive to print surface |
DE60010050T2 (en) | 1999-02-05 | 2005-07-14 | Essex Epecialty Products Llc, Auburn Hills | POLYURETHANE SEALING COMPOSITION |
JP5059274B2 (en) | 2000-08-07 | 2012-10-24 | ダウ グローバル テクノロジーズ エルエルシー | One-part moisture curable polyurethane adhesive |
US6617371B2 (en) * | 2001-06-08 | 2003-09-09 | Addison Clear Wave, Llc | Single component room temperature stable heat-curable acrylate resin adhesive |
MXPA04004762A (en) * | 2001-11-29 | 2004-07-30 | Dow Global Technologies Inc | Method of bonding a window to a substrate without a primer. |
CA2547767A1 (en) | 2003-12-10 | 2005-06-30 | Dow Global Technologies Inc. | System for bonding glass into a structure |
US7494540B2 (en) | 2004-12-15 | 2009-02-24 | Dow Global Technologies, Inc. | System for bonding glass into a structure |
US7763668B2 (en) * | 2005-03-23 | 2010-07-27 | Imtech, Inc. | Curable thermally ejectable printing fluid |
US7781493B2 (en) | 2005-06-20 | 2010-08-24 | Dow Global Technologies Inc. | Protective coating for window glass |
US7786183B2 (en) * | 2005-06-20 | 2010-08-31 | Dow Global Technologies Inc. | Coated glass articles |
US7345130B2 (en) * | 2005-10-25 | 2008-03-18 | Dow Global Technologies Inc. | Silane functional prepolymer and isocyanate functional prepolymer blend based adhesive composition |
US7939161B2 (en) * | 2006-12-19 | 2011-05-10 | Dow Global Technologies Llc | Encapsulated panel assemblies and methods for making same |
EP2122638B1 (en) | 2006-12-19 | 2012-11-07 | Dow Global Technologies LLC | Improved composites and methods for conductive transparent substrates |
JP5264766B2 (en) | 2006-12-19 | 2013-08-14 | ダウ グローバル テクノロジーズ エルエルシー | Adhesion promoting additives and methods for improving coating compositions |
US7819964B2 (en) | 2007-02-16 | 2010-10-26 | Dow Global Technologies Inc. | System for bonding glass into a structure |
CA2659367C (en) * | 2007-05-30 | 2011-08-23 | Dow Global Technologies Inc. | Method of preparing glass and ceramic enamels on glass for adhesive bonding |
KR101572276B1 (en) * | 2007-07-23 | 2015-11-26 | 다우 글로벌 테크놀로지스 엘엘씨 | Two part polyurethane curable composition having substantially consistent g-modulus across the range of use temperatures |
EP2225339B1 (en) | 2007-12-18 | 2016-06-29 | Dow Global Technologies LLC | Protective coating for window glass having enhanced adhesion to glass bonding adhesives |
WO2010021793A1 (en) * | 2008-08-22 | 2010-02-25 | Dow Global Technologies Inc. | Adhesive composition adapted for bonding large mass parts to structures |
WO2010096110A1 (en) * | 2008-10-29 | 2010-08-26 | Dow Global Technologies, Inc. | Low energy surface bonding system containing a primer with long open time |
WO2011112440A1 (en) | 2010-03-08 | 2011-09-15 | Dow Global Technologies Llc | Water based primer composition for isocyante and silane functional adhesives |
EP2635625B1 (en) | 2010-11-01 | 2016-11-30 | Dow Brasil S.A. | Polyolefins having one or more surfaces modified to improve adhesion of polyisocyanate functional adhesives thereto |
CN103261254B (en) | 2010-12-20 | 2015-02-11 | 陶氏环球技术有限责任公司 | Curable compositions containing isocyanate functional components having improved durability in the cured state |
WO2012151086A1 (en) | 2011-05-03 | 2012-11-08 | Dow Global Technologies Llc | Dual cure adhesive useful for bonding to glass |
US9296932B2 (en) | 2011-05-03 | 2016-03-29 | Dow Global Technologies Llc | Accelerated cure composition containing an isocyanate functional prepolymer |
US9499727B2 (en) | 2012-07-16 | 2016-11-22 | Dow Global Technologies Llc | Curable compositions containing isocyanate functional components having improved durability |
US9416301B2 (en) | 2012-11-08 | 2016-08-16 | Dow Global Technologies Llc | Ultrafast dual cure adhesive useful for bonding to glass |
US9428678B2 (en) | 2012-12-21 | 2016-08-30 | Dow Global Technologies Llc | Fast curing adhesive useful for bonding to glass |
JP6634027B2 (en) | 2014-05-08 | 2020-01-22 | ダウ グローバル テクノロジーズ エルエルシー | Accelerated curing of moisture-curable polyurethane adhesive compositions useful for bonding glass |
US20210207011A1 (en) | 2016-02-17 | 2021-07-08 | Dow Global Technologies Llc | Compositions containing isocyanate functional prepolymers and quaternary ammonum modified nanoclays |
CN109642117B (en) | 2016-04-19 | 2021-10-01 | 陶氏环球技术有限责任公司 | Long open time water-based primer compositions for isocyanate and silane functional adhesives |
US11499075B2 (en) | 2017-09-29 | 2022-11-15 | Ddp Specialty Electronics Materials Us, Llc | Isocyanate functional adhesive which bonds primerless to silanated acrylic polyol based coatings |
CN114008166A (en) | 2019-06-25 | 2022-02-01 | Ddp特种电子材料美国有限责任公司 | Accelerated cure polyurethane adhesive compositions |
EP4049841A1 (en) * | 2021-02-26 | 2022-08-31 | Cubicure GmbH | Hybrid resin composition |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3970505A (en) * | 1973-01-15 | 1976-07-20 | Loctite Corporation | Anaerobic compositions and surface activator therefor |
US4007323A (en) * | 1975-10-28 | 1977-02-08 | Loctite Corporation | Initiator for anaerobic compositions |
US4100141A (en) * | 1976-07-02 | 1978-07-11 | Loctite (Ireland) Limited | Stabilized adhesive and curing compositions |
EP0114117A1 (en) * | 1983-01-18 | 1984-07-25 | Loctite Corporation | Rapid cure acrylic monomer systems |
US4717739A (en) * | 1982-11-05 | 1988-01-05 | Deltaglass S.A. | Radiation curable clear urethane acrylate adhesive with acrylic acid monoacrylates, and optional multiacrylate |
EP0290147A2 (en) * | 1987-04-13 | 1988-11-09 | Dymax Corporation | Radiation-cured adhesive system containing perester/tautomeric acid adhesion promoter |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2718516A (en) * | 1952-11-08 | 1955-09-20 | Rohm & Haas | Isocyanato esters of acrylic, methacrylic, and crotonic acids |
US2821544A (en) * | 1954-04-26 | 1958-01-28 | Bayer Ag | Production of alkylisocyanate esters of 2-alkenoic acids |
US4174307A (en) * | 1972-12-14 | 1979-11-13 | Polychrome Corporation | Room-temperature-radiation-curable polyurethane |
US4089763A (en) * | 1973-04-24 | 1978-05-16 | Imperial Chemical Industries Limited | Method of repairing teeth using a composition which is curable by irradiation with visible light |
US4097439A (en) * | 1977-02-08 | 1978-06-27 | E. I. Du Pont De Nemours And Company | Polyurethane coating composition curable by addition polymerization |
US4297448A (en) * | 1979-10-17 | 1981-10-27 | Ford Motor Company | Coating composition of aminoplast, hydroxy polymers and vinylic monomers |
US4390645A (en) * | 1979-11-23 | 1983-06-28 | The Dow Chemical Company | Stable dispersions of polymers in polyfunctional compounds having a plurality of active hydrogens and polyurethanes therefrom |
US4317894A (en) * | 1979-12-11 | 1982-03-02 | Ppg Industries, Inc. | Low temperature cure coating compositions |
US4318833A (en) * | 1980-05-16 | 1982-03-09 | Inmont Corporation | Water reducible coating compositions of acrylic-urethane polymers |
JPS59173809A (en) * | 1983-03-22 | 1984-10-02 | Nippon Cable Syst Inc | Operating device for control cable |
US4703089A (en) * | 1984-04-10 | 1987-10-27 | Damico Dennis J | Structural adhesive formulations |
US4644030A (en) * | 1985-02-01 | 1987-02-17 | Witco Corporation | Aqueous polyurethane - polyolefin compositions |
JPS6254716A (en) * | 1985-09-04 | 1987-03-10 | Nippon Synthetic Chem Ind Co Ltd:The | Air-drying resin composition |
US4775727A (en) * | 1986-04-30 | 1988-10-04 | Bp Chemicals Limited | Rapid cure acrylic adhesive compositions |
US4769419A (en) * | 1986-12-01 | 1988-09-06 | Dawdy Terrance H | Modified structural adhesives |
US4876308A (en) * | 1988-02-18 | 1989-10-24 | Gencorp Inc. | Polyurethane adhesive for a surface treatment-free fiber reinforced plastic |
AU4821390A (en) * | 1990-01-02 | 1991-07-24 | Guertin Bros. Coatings And Sealants, Ltd. | Nco-free resins useful as a substitute for polyurethanes |
-
1990
- 1990-01-16 US US07/464,828 patent/US5063269A/en not_active Expired - Lifetime
-
1991
- 1991-01-14 EP EP91100367A patent/EP0439040A1/en not_active Withdrawn
- 1991-01-15 ZA ZA91293A patent/ZA91293B/en unknown
- 1991-01-15 CA CA002034166A patent/CA2034166C/en not_active Expired - Fee Related
- 1991-01-15 AU AU69335/91A patent/AU628769B2/en not_active Ceased
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3970505A (en) * | 1973-01-15 | 1976-07-20 | Loctite Corporation | Anaerobic compositions and surface activator therefor |
US4007323A (en) * | 1975-10-28 | 1977-02-08 | Loctite Corporation | Initiator for anaerobic compositions |
US4100141A (en) * | 1976-07-02 | 1978-07-11 | Loctite (Ireland) Limited | Stabilized adhesive and curing compositions |
US4717739A (en) * | 1982-11-05 | 1988-01-05 | Deltaglass S.A. | Radiation curable clear urethane acrylate adhesive with acrylic acid monoacrylates, and optional multiacrylate |
EP0114117A1 (en) * | 1983-01-18 | 1984-07-25 | Loctite Corporation | Rapid cure acrylic monomer systems |
EP0290147A2 (en) * | 1987-04-13 | 1988-11-09 | Dymax Corporation | Radiation-cured adhesive system containing perester/tautomeric acid adhesion promoter |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0591803A1 (en) * | 1992-10-05 | 1994-04-13 | BASF Aktiengesellschaft | Cartridge for chemical fixing engineering |
US6355317B1 (en) | 1997-06-19 | 2002-03-12 | H. B. Fuller Licensing & Financing, Inc. | Thermoplastic moisture cure polyurethanes |
WO1999033930A1 (en) * | 1997-12-24 | 1999-07-08 | Essex Specialty Products, Inc. | Primerless adhesive for a painted surface |
EP1426390A2 (en) * | 2002-11-14 | 2004-06-09 | Rohm And Haas Company | Curable clay composition: composition, processes, and uses thereof |
EP1426390A3 (en) * | 2002-11-14 | 2004-06-16 | Rohm And Haas Company | Curable clay composition: composition, processes, and uses thereof |
EP1642914A1 (en) * | 2002-11-14 | 2006-04-05 | Rohm and Haas Company | Curable clay composition : composition, processes, and uses thereof |
Also Published As
Publication number | Publication date |
---|---|
CA2034166C (en) | 2001-04-10 |
CA2034166A1 (en) | 1991-07-17 |
AU6933591A (en) | 1991-07-18 |
US5063269A (en) | 1991-11-05 |
ZA91293B (en) | 1992-09-30 |
AU628769B2 (en) | 1992-09-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5063269A (en) | One-part primerless adhesive | |
US3772404A (en) | Resins | |
US4018851A (en) | Curable poly(alkylene) ether polyol-based grafted resins having improved properties | |
US4232133A (en) | Polyisocyanurate containing molding compositions | |
US3291859A (en) | Block copolymers formed by the reaction of an isocyanate-terminated polymer with a dual functional free radical initiator and an ethylenically unsaturated monomer | |
JPS58147477A (en) | Adhesive composition for structure | |
JPH0126387B2 (en) | ||
EP0632077A2 (en) | Moisture-curable polyurethane adhesive | |
CN109071753B (en) | Styrene-free reactive diluents for urethane acrylate resin compositions | |
JP2019507231A (en) | Process for making urethane acrylate | |
US3823051A (en) | B-stage polyurethane compositions | |
US4439577A (en) | Modified polyurethane liquid polymer compositions | |
JPH0678515B2 (en) | Solvent-free hot melt-polyurethane adhesive composition | |
US5482648A (en) | Catalyst system for adherent rigid foam | |
US4233424A (en) | Process for the production of bead polymers | |
US4159376A (en) | Isocyanurates from unsaturated monohydric alcohols and polyisocyanates | |
US4772658A (en) | Low viscosity copolymer polyisocyanates | |
EP0665278B1 (en) | High performance vinyl laminating adhesive | |
KR20180120190A (en) | A curable urethane acrylate composition having a bimodal molecular weight distribution | |
JPH0671833A (en) | Laminate of aromatic polycarbonate | |
JPH06145636A (en) | Urethane acrylate adhesive | |
EP0530302B1 (en) | Composition to be used in the resin injection moulding technique, containing low molecular weight compounds jointly forming a hybrid network | |
US4463158A (en) | Modified polyurethane liquid polymer compositions | |
US4552943A (en) | Modified polyurethane liquid polymer compositions | |
EP0076126B1 (en) | Modified polyurethane liquid polymer compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19920117 |
|
17Q | First examination report despatched |
Effective date: 19930705 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
18W | Application withdrawn |
Withdrawal date: 19940603 |